| 1. |
- Ahlkvist, Johan, et al.
(författare)
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Macro-molecules as a source of levulinic acid
- 2014
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Ingår i: International Review of Chemical Engineering. - : Praise Worthy Prize. - 2035-1755. ; 16:1, s. 44-58
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Tidskriftsartikel (refereegranskat)abstract
- The production of levulinic acid from biomass and macromolecules has been reviewed. It was concluded that the most important parameters in the one-pot hydrolysis of biomass, also including dehydration of glucose to hydroxymethylfurfural as well as its further rehydration to formic and levulinic acids, respectively, are the reaction temperature, initial reactant concentration, acid type as well as the raw material applied. The theoretical maximum yield can hardly be obtained due to formation of humins. Further, the optimum reaction conditions as well as the influence of the catalyst and biomass type are also discussed.
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| 2. |
- Anugwom, Ikenna, et al.
(författare)
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Switchable ionic liquids as delignification solvents for lignocellulosic materials
- 2014
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Ingår i: ChemSusChem. - : John Wiley & Sons. - 1864-5631 .- 1864-564X. ; 7:4, s. 1170-1176
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Tidskriftsartikel (refereegranskat)abstract
- The transformation of lignocellulosic materials into potentially valuable resources is compromised by their complicated structure. Consequently, new economical and feasible conversion/fractionation techniques that render value-added products are intensely investigated. Herein an unorthodox and feasible fractionation method of birch chips (B. pendula) using a switchable ionic liquid (SIL) derived from an alkanol amine (monoethanol amine, MEA) and an organic super base (1,8-diazabicyclo-[5.4.0]-undec-7-ene, DBU) with two different trigger acid gases (CO2 and SO2 ) is studied. After SIL treatment, the dissolved fractions were selectively separated by a step-wise method using an antisolvent to induce precipitation. The SIL was recycled after concentration and evaporation of anti-solvent. The composition of undissolved wood after MEA-SO2 -SIL treatment resulted in 80 wt % cellulose, 10 wt % hemicelluloses, and 3 wt % lignin, whereas MEA-CO2 -SIL treatment resulted in 66 wt % cellulose, 12 wt % hemicelluloses and 11 wt % lignin. Thus, the MEA-SO2 -SIL proved more efficient than the MEA-CO2 -SIL, and a better solvent for lignin removal. All fractions were analyzed by gas chromatography (GC), Fourier transform infrared spectroscopy (FT-IR), (13) C nuclear magnetic resonance spectroscopy (NMR) and Gel permeation chromatography (GPC).
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| 3. |
- Anugwom, Ikenna, et al.
(författare)
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Switchable ionic liquids (SILs) based on glycerol and acid gases
- 2011
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Ingår i: RSC Advances. - : The Royal Society of Chemistry. - 2046-2069. ; 1:3, s. 452-457
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Tidskriftsartikel (refereegranskat)abstract
- New types of switchable ionic liquids (SILs), containing 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU), glycerol and an acid gas (CO2, SO2), were synthesized and characterized in this study. [DBU][Carbonate] or [sulfonate] were easily synthesized from a non-ionic mixture of molecular organic polyol and amidine base upon bubbling of an acid gas (CO2, SO2). Moreover, they were switched back to the original molecular solvents by flushing out the acid gas (CO2, SO2) by heating and/or bubbling an inert gas such as N2 through it. The structures of the SILs were confirmed by NMR and FTIR. The change from low polarity (molecular solvent) to high polarity (Switchable Ionic Liquid, SIL) was also indicated by the changes in properties, such as viscosity and miscibility with different organic solvents. The decomposition temperatures of the SILs were determined by means of Thermo Gravimetric Analysis (TGA) and gave values in the range of 50 °C and 120 °C for DBU-glycerol-CO2 (SIL1) and DBU-glycerol-SO2 (SIL2), respectively. Due to the reasonable decomposition temperatures, these novel SILs can be employed in multiple applications.
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| 4. |
- Anugwom, Ikenna, et al.
(författare)
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The effect of switchable ionic liquid (SIL) treatment on the composition and crystallinity of birch chips (Betula pendula) using a novel alkanol amine-organic superbase-derived SIL
- 2014
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Ingår i: Green Processing and Synthesis. - : Walter de Gruyter GmbH. - 2191-9542 .- 2191-9550. ; 3:2, s. 147-154
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Tidskriftsartikel (refereegranskat)abstract
- Two-step treatment of birch chips (Betula pendula) was tested using diethanolamine (DEA)-1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU)-CO2-switchable ionic liquid (SIL), resulting in a 23% weight reduction in 24 h. The weight of the chips was reduced to 32% of their initial weight upon the second treatment with fresh SIL. SIL to wood ratio of 5:1, at 100°C for 24 h, without stirring, was applied in both steps. The relative amount of wood lignin reduced from 24% to 14% after two treatment cycles. The relative amount of cellulose of the undissolved fraction after SIL treatment increased from 43% (native birch wood) to 68% after the second cycle. Also, the undissolved material was efficiently fibrillated. The dissolved materials recovered from spent SIL, after treatment, contained high xylan content, about 90% of the total hemicelluloses, which was 85% of the recovered material. The powder X-ray diffraction (XRD) results revealed that the crystallinity of the undissolved material increased slightly, indicating dissolution of the amorphous material. Moreover, transformation of cellulose form I to form II in the remaining undissolved chips was not observed.
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| 5. |
- Conte, Ricardo Pezoa, et al.
(författare)
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Bioethanol production from the green alga ulva rigida and the brown algae macrocystis pyrifera
- 2015
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Ingår i: NWBC 2015. - : VTT Technical Research Centre of Finland. - 9789513883539 ; , s. 319-325
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Konferensbidrag (refereegranskat)abstract
- Macroalgae are suitable bioresources to be explored as raw material for bioethanol production, as about 40 wt.% of its mass is composed of carbohydrates and they completely lack lignin. In this work the simultaneous saccharification and fermentation (SSF) of the green alga Ulva rigida and the brown alga Macrocystis pyrifera was performed. The algae were initially pretreated in deionized water or diluted sulfuric acid at 125°C in an autoclave for 60 min, respectively. Commercial cellulolytic enzymes and yeast were used for ethanol production. The carbohydrate composition of the fresh alga, pretreated alga and glucose and ethanol concentrations in the SSF processing are given. The water pretreatment solubilized 82 wt.% of the ulvan (rhamno-glucuroxylan) contained in U. rigida and 73 wt.% of the glucan remained in the residue. The diluted acid treatment removed 93 wt.% of the carbohydrates contained in U. rigida. The SSF of U. rigida pretreated with water produced 0.47 g EtOH/g sugar, with a 92 wt.% theoretical yield. In turn, water and diluted acid pretreatment of M. pyrifera increased 8.4 and 14.8 fold the carbohydrate content in the pretreated alga compared to the SSF of the fresh alga. The SSF of M. pyrifera pretreated with dilute sulfuric acid produced 0.15 g EtOH/g sugar, 29 wt.% theoretical yield. The production of ethanol was demonstrated for U. rigida and M. pyrifera with mild pretreatments. Especially in case of U. rigida simple water treatment allows to isolate ulvan for other purposes and efficiently ferment the remaining fibers.
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| 6. |
- Eta, Valerie, et al.
(författare)
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Kinetics of dimethyl carbonate synthesis from methanol and carbon dioxide over ZrO2–MgO catalyst in the presence of butylene oxide as additive
- 2011
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Ingår i: Applied Catalysis A. - : Elsevier. - 0926-860X .- 1873-3875. ; 404:1-2, s. 39-46
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Tidskriftsartikel (refereegranskat)abstract
- A kinetic investigation of dimethyl carbonate (DMC) synthesis from methanol and CO2 over ZrO2–MgO was performed by using butylene oxide as a chemical trap for the water formed during the reaction. The effect of the catalyst amount, the stirring speed, the temperature, as well as the amount of butylene oxide on the reaction rate and the selectivity to DMC was studied. The analysis of the reaction pathway suggests that DMC and butylene glycol are formed via the reaction of adsorbed mono-methoxycarbonate intermediate and methoxybutanol or methanol. A kinetic model was developed based on the reaction mechanism and it was in agreement with the experimental data. The apparent activation energy for the formation of DMC was 62 kJ/mol.
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| 7. |
- Eta, Valerie, et al.
(författare)
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Synthesis of dimethyl carbonate from methanol and carbon dioxide : Circumventing thermodynamic limitations
- 2010
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Ingår i: Industrial & Engineering Chemistry Research. - : American Chemical Society. - 0888-5885 .- 1520-5045. ; 49:20, s. 9609-17
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Tidskriftsartikel (refereegranskat)abstract
- The synthesis of dimethyl carbonate from methanol and CO2 catalyzed by ZrO2 doped with KCl was investigated using chemical traps for water to circumvent thermodynamic limitations. The reaction, promoted by magnesium, occurred via the formation of carbonated magnesium methoxide (CMM) which adsorbed on the surface of ZrO2. The surface migration of the oxygen atom of ZrO2 to the surface methoxy groups of CMM resulted in the formation of dimethyl carbonate. The resulting MgO then reacted with methanol forming water and regenerating magnesium methoxide. The water formed reacted with the dehydrating agent, thus shifting the equilibrium toward a higher yield of DMC. The yield of 7.2 mol % DMC and 13.6 mol % conversion of methanol was obtained when methanol reacted with CO2 at 150 °C and 9.5 MPa for 8 h. The plausible reaction pathway is described.
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| 8. |
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| 9. |
- Jogi, Ramakrishna, et al.
(författare)
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Biocrude production through hydro‐liquefaction of wood biomass in supercritical ethanol using iron silica and iron Beta zeolite catalysts
- 2019
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Ingår i: Journal of chemical technology and biotechnology (1986). - : John Wiley & Sons. - 0268-2575 .- 1097-4660. ; 94:11, s. 3736-3744
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Tidskriftsartikel (refereegranskat)abstract
- BACKGROUND: In the production of biofuels from lignocellulosic material, biocrude plays a key role. The present work deals with the biocrude production through hydrothermal liquefaction (HTL) of birch wood in supercritical ethanol over 5 wt. % Fe‐H‐Beta‐150 (SiO2 to Al2O3 ratio of 150) or 5 wt. % Fe‐SiO2 catalyst.RESULTS: The liquid and solid products were characterized with various analytical techniques such as GC‐MS, GC‐FID, SEC, ICP‐MS, p‐XRD, SEM, and solid‐state 13C MAS NMR respectively. The results revealed that 5 wt. % Fe‐H‐Beta‐150, a strongly Brønsted acidic catalyst, enhanced the biocrude formation when compared with a non‐acidic 5 wt. % Fe‐SiO2 catalyst. Hemicellulose and lignin degradation occurred resulting in formation of mainly sugars, acids‐esters and phenolic compounds in liquid phase. The gaseous atmosphere of hydrogen also enhanced the degradation of biomass. The biocrude yield from birch was 25 wt. % over 5 wt. % Fe‐H‐Beta‐150. The Brønsted acidic catalyst gave higher dissolution efficiency and its clear catalytic effect was observed in comparison to non‐acidic 5 wt. % Fe‐SiO2. The degradation level of lignin in presence of 5 wt. % Fe‐H‐Beta‐150 was high 68 wt. % aromatic products were formed, while only 38 wt. % was obtained with 5 wt. % Fe‐SiO2.CONCLUSIONS: Hydrogen atmosphere enhances the fractionation of birch wood when compared to argon atmosphere. 5 wt. % Fe‐H‐Beta‐150 catalyst enhanced very strongly the degradation of hemicellulose and lignin in biomass to sugars and acid‐esters as well as phenolic compounds, respectively compared to the non‐acidic 5 wt. % Fe‐SiO2 catalyst.
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| 10. |
- Jogi, Ramakrishna, et al.
(författare)
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Liquefaction of Lignocellulosic Biomass into Phenolic Monomers and Dimers Over Multifunctional Pd/Nbopo4 Catalyst
- 2022
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Ingår i: SSRN Electronic Journal. - : Elsevier BV. - 1556-5068.
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- For the first time, a tandem catalytic material namely 5 wt. % Pd/NbOPO 4 was utilized in the depolymerization of wood in supercritical-ethanol under low initial-hydrogen pressure. The experiments were conducted under various experimental conditions, wood fractionation was executed with fresh, and acetone extracted birch. A comprehensive analysis was performed to elucidate the dissolution efficiency and achieved product distribution. The results indicated fresh birch, 34 wt. % of lignin monomer yield with 84 wt. % delignification efficiency were obtained while extracted wood, 35 wt. % of lignin monomer yield with 78 wt. % delignification efficiency was achieved. The total lignin monomer content extracted from the fresh birch is composed of 76.9 wt. % of dimethoxyphenols and 16.5 wt. % of monomers with the guaiacol structure. Among the dimethoxyphenols, major homosyringaldehyde (61.9 wt. %). Where extracted wood, 93.2 wt. % of dimethoxyphenols (63.6 wt. % homosyringaldehyde) and guaiacol-monomers (6.8 wt. %). It was concluded that the depolymerization occurred via breaking of the ether bonds in lignin, including ether hydrolysis by Lewis acid sites over the solid acid catalyst and with subsequent deoxygenation of monophenols over Pd. In addition, an extraction process was proposed to extract the aromatic fraction from the obtained biocrude.
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